金属玻璃流变的扩展弹性模型

玻璃-液体转变现象,简称玻璃转变,被诺贝尔物理学奖获得者安德森教授评为最深奥与重要的凝聚态物理问题之一.金属玻璃作为典型的非晶态物质,具有与液体相似的无序原子结构,因此又称为冻结了的液态金属,是研究玻璃转变问题的理想模型材料.当加热至玻璃转变温度,或者加载到力学屈服点附近时,金属玻璃将会发生流动.由于热或应力导致的流动现象对金属玻璃的应用具有重要意义.本文简要回顾了金属玻璃流变现象,综述了流变扩展弹性模型的研究进展和未来发展趋势.     

Ultrasonic,FTIR and thermal investigations of SiO2–Na2O–CaO–P2O5 glasses doped with CeO2

The longitudinal and shear ultrasonic wave velocities for different compositions of SiO₂–Na₂O–CaO–P₂O₅ glasses were measured at room temperature (305 K) using a pulse-echo method at a frequency of 4 MHz. The elastic moduli, Poisson's ratio, microhardness, Debye temperature and other ultrasonic parameters were obtained from experimental data and analyzed using bond compression theory. By calculating the number of network bonds per unit volume, the average stretching constant, and the average ring size, information about the structure of the glass can be deduced. Structural changes after doping with CeO₂ were investigated by FTIR spectroscopy, and by measurements of the thermal expansion coefficient, glass transition and softening temperature to throw more light on the characterization of these glasses.     

Elastic properties and spectroscopic studies of lithium lead borate glasses

Elastic properties of xLi₂O — 20PbO — (80-x)B₂O₃ glasses have been measured at a frequency of 10 MHz using X-cut and Y-cut quartz transducers. The trends in the variation of elastic moduli, Poisson’s ratio and Debye temperature have been studied. The elastic moduli namely longitudinal and young’s modulus show strong linear dependence while bulk and shear modulus vary marginally as a function of Li₂O concentration. The Poisson’s ratio is found to be almost constant and Debye temperature increases with the increase of Li₂O concentration. IR, MAS-NMR and glass transition temperature studies have been also carried out. Glass transition temperature is found to increase with increase of Li₂O concentration. IR and MAS-NMR spectra show characteristic features of borate network and systematic change as a function of Li₂O concentration. The variation in the elastic properties and structural features of IR and MAS-NMR indicate that Pb²⁺ ions are likely to occupy network forming positions in this glass system. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Vorticity alignment and negative normal stresses in sheared attractive emulsions

Attractive emulsions near the colloidal glass transition are investigated by rheometry and optical microscopy under shear. We find that (i) the apparent viscosity eta drops with increasing shear rate, then remains approximately constant in a range of shear rates, then continues to decay; (ii) the first normal stress difference N1 transitions sharply from nearly zero to negative in the region of constant shear viscosity; and (iii) correspondingly, cylindrical flocs form, align along the vorticity, and undergo a log-rolling movement. An analysis of the interplay between steric constraints, attractive forces, and composition explains this behavior, which seems universal to several other complex systems.     

Ultrasonic studies on polystyrene/styrene butadiene rubber polymer blends filled with glass fiber and talc

The compatibility of solid blends: PS/SBR, PS/SBR filled with glass fiber and PS/SBR filled with talc were studied using ultrasonic pulse echo technique. Measurements were carried out at room temperature (298 K) and a frequency of 3 MHz. The ultrasonic velocity for the compressional wave and that for shear wave have been measured to obtain the elastic moduli data by knowing of density. The variation of ultrasonic wave velocities and elastic moduli with weight percent of the blend was found to be linear in PS/SBR blend, indicating some degree of compatibility but the drawback of elastic moduli indicate incompatibility of the system blend, while it deviates from linearity in blends of PS/SBR filled with glass fiber and talc but the increase in elastic moduli indicates that there is an increase in degree of compatibility between PS and SBR due to adding of glass fiber or talc. The ultrasonic absorptions for longitudinal wave in the temperature range from 298 to 423 K in the studied system were measured using ultrasonic pulse echo technique. Typical results showing the temperature dependence of the ultrasonic absorption at frequencies of 1, 2, 3 and 5 MHz are illustrated for all samples of the different compositions. The study of compositional and temperature dependence of the ultrasonic absorption in the present studied blends reveals the same behavior of the compatibility degree of the blends. Density data of the blends confirmed the ultrasonic results. Also the correlation between hardness and elastic moduli for the present blend systems has been studied.     

Activated bond-breaking processes preempt the observation of a sharp glass-glass transition in dense short-ranged attractive colloids

We study-using molecular dynamics simulations-the temperature dependence of the dynamics in a dense short-ranged attractive colloidal glass to find evidence of the kinetic glass-glass transition predicted by the ideal mode coupling theory. According to the theory, the two distinct glasses are stabilized, one by excluded volume and the other by short-ranged attractive interactions. By studying the density autocorrelation functions, we discover that the short-ranged attractive glass is unstable. Indeed, activated bond-breaking processes slowly convert the attractive glass into the hard-sphere one, preempting the observation of a sharp glass-glass transition.     

Irreversible structural relaxation in a bulk Pd-Cu-Ni-P metallic glass

The evolution of the shear modulus and the damping decrement during irreversible structural relaxation in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in a temperature range below the glass transition temperature has been studied with an inverse torsion pendulum at a frequency of ～25 Hz. It is shown that the irreversible relaxation can be recovered via quenching from temperatures above the glass transition temperature. The spectrum shape, the characteristic activation energies, and the attempt frequencies of the irreversible structural relaxation are estimated.     

Vibrational anomalies and marginal stability of glasses

The experimentally measured vibrational spectrum of glasses strongly deviates from that expected in Debye’s elasticity theory: The density of states deviates from Debye’s ω² law (“boson peak”), the sound velocity shows a negative dispersion in the boson-peak frequency regime, and there is a strong increase in the sound attenuation near the boson-peak frequency. A generalized elasticity theory is presented, based on the model assumption that the shear modulus of the disordered medium fluctuates randomly in space. The fluctuations are assumed to be uncorrelated and have a certain distribution (Gaussian or otherwise). Using field-theoretical techniques one is able to derive mean-field theories for the vibrational spectrum of a disordered system. The theory based on a Gaussian distribution uses a self-consistent Born approximation (SCBA),while the theory for non-Gaussian distributions is based on a coherent-potential approximation (CPA). Both approximate theories appear to be saddle-point approximations of effective replica field theories. The theory gives a satisfactory explanation of the vibrational anomalies in glasses. Excellent agreement of the SCBA theory with simulation data on a soft-sphere glass is reached. Since the SCBA is based on a Gaussian distribution of local shear moduli, including negative values, this theory describes a shear instability as a function of the variance of shear fluctuations. In the vicinity of this instability, a fractal frequency dependence of the density of states and the sound attenuation ∝ ω^1+a is predicted with a ? 1/2. Such a frequency dependence is indeed observed both in simulations and in experimental data. We argue that the observed frequency dependence stems from marginally stable regions in a glass and discuss these findings in terms of rigidity percolation.     

Dynamic Rheological Behavior of Copolymerized Linear Low-Density Polyethylenes: Effect of Molecular Weight and Its Distribution

The change of storage moduli (G′), loss moduli (G″), zero shear viscosity, and complex viscosity were studied for a series of butene and hexene copolymerized linear low-density polyethylenes (LLDPEs) with various characteristics by investigating the dynamic rheological behaviors. It was found that: (1) the dependence of the complex viscosity on the weight average molecular weight did not follow the Raju equation; (2) the slopes of the G′～ω and G″～ω curves in the low-frequency regions not only were smaller than those of the polymers with monodisperse molecular weight, but also decreased with the relative molecular weight increasing or its distribution broadening; (3) the dynamic storage moduli G′ were more sensitive to the shear rate than the dynamic loss moduli G″; (4) the change of the dynamic moduli was directly correlated with the orientation and disorientation of the chain segments, which is influenced by the frequency or shear rate, the temperature, the molecular weight, and the molecular weight distribution; and (5) the comonomer types showed little effect on the frequency dependence of the dynamic moduli at different temperatures.     

Mechanical, vibrational, and dynamical properties of amorphous systems near jamming

Amorphous systems undergo the jamming transition when the density increases, temperature drops, or external shear stress decreases, as described by the jamming phase diagram which was proposed to unify different processes such as the glass transition, random close packing, and yielding under shear stress. At zero temperature and shear stress, the jamming transition occurs at a critical density at Point J. In this paper, we review recent studies of the material properties of marginally jammed solids and the glassy dynamics in the vicinity of Point J. As the only singular point in the jamming phase diagram, Point J exhibits special criticality in both mechanical and vibrational quantities. Dynamics approaching the glass transition in the vicinity of Point J show critical scalings, suggesting that the molecular glass transition and the colloidal glass transition are equivalent in the hard sphere limit. All these studies shed light on the long-standing puzzles of the glass transition and unusual properties of amorphous solids.     

Temperature effect on the elastic properties of yttrium garnet ferrite Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript>

The Young’s moduli along the [100] and [110] crystallographic directions and the shear modulus along the [100] direction in a high-purity yttrium garnet ferrite single crystal are measured in the temperature range from 20 to 600°C. All the independent elastic constants are calculated for this temperature range. The behavior of the elastic moduli and elastic anisotropy factor is analyzed in the vicinity of the critical temperature of the magnetic phase transition.     

Investigation of the creep and glass transition of elastomers by the microindentation method: Epoxy resin and related nanocomposites

The experimental procedure and theoretical grounds of the applicability of the microindentation method as one of the effective techniques of relaxation spectrometry of solid-state polymers have been developed. It has been shown that the glass transition temperature and rheological parameters of the material (unrelaxed and relaxed elastic moduli, strain viscosity coefficients) can be determined from measurements of the temperature dependence of the microhardness of polymers in a high-elasticity state and in the glass transition region with the recording of the long-term creep under the indenter. These measurements provide sufficient information for the formulation of a rheological model of the material under investigation. The results of these measurements are supplemented by the concepts of thermally activated motion of molecular segments as the microscopic mechanism of structural relaxation in polymers, which makes it possible to obtain empirical estimates for the activation energies and vibrational frequencies of the molecular segments. The method is implemented in experiments on the microindentation of the epoxy resin and its composites with the addition of carbon nanotubes in the temperature range 230–300 K. The glass transition of these polymers has been observed at temperatures near 260 K, the unrelaxed and relaxed Young’s moduli have been measured, and two thermally activated relaxation processes determining the glass transition, as well as the shortterm and long-term creeps of these materials (α- and α′-processes), have been revealed.     

The synergetic theory of the glass transition in liquids

The glass transition is treated as a spontaneous emergence of the shear components of strain and stress elastic fields upon cooling a liquid at a rate exceeding the critical value. The stationary elastic strains and stresses and the effective relaxation time are determined within the adiabatic approximation. It is shown that the glass transition process occurs through the mechanism of a first-order kinetic transition with allowance made for the strain dependence of the shear modulus. The critical cooling rate turns out to be proportional to the thermal diffusivity and unrelaxed shear modulus and inversely proportional to the temperature derivative of the relaxed shear modulus and the square of the heat conductivity length of the sample.     

Behaviour of ultrasonic velocities in amorphous Se90Ge10 and Se85Ge15 alloys near their glass transition

Precise measurements of 10 MHz frequency longitudinal and shear wave velocities are reported in amorphous SeGe alloys near their glass transition temperature T _g . There is a sharp decrease of the velocities near T _g , but the reduction in velocities appears smaller than expected.     

Acoustic anisotropy and birefringence in fibre-reinforced composite materials

All nine elastic moduli of an orthotropic composite material, namely, polypropylene reinforced with glass fiber, are determined from the measured values of the bulk acoustic wave velocities along specific directions in the planes of symmetry of the material. These data are used to calculate the angular dependences of phase velocities, polarization vectors, and directions of ray velocities of bulk waves in the composite. It is demonstrated that the difference in the velocities of shear waves polarized along and across the glass fiber gives rise to an acoustic birefringence and can lead to an elliptical polarization of waves. The measurement of the phase velocities of shear waves as functions of the wave polarization is suggested as a method for the determination of the fiber orientation in a composite material.     

DSC and elastic moduli studies on tellurite-vanadate glasses containing antimony oxide

xSb₂O₃-40TeO₂-(60 − x) V₂O₅ glasses with 0 ≤ x ≤ 10 (in mol%) have been prepared by rapid- melt quenching method. DSC curves of these ternary glasses have been investigated. The glass transition properties that have been measured and reported in this paper, include the glass transition temperature (T _g ), glass transition width (ΔT _g ), heat capacity change at glass transition (ΔC _P ) and fragility (F). Thermal stability, Poisson’s ratio, fragility and glass forming tendency of these glasses have been estimated, to determine relationship between chemical composition and the thermal stability or to interpret the structure of glass. In addition, Makishima and Makenzie’s theory was applied for determination of Young’s modulus, bulk modulus and shear modulus, indicating a strong relation between elastic properties and structure of glass. Generally, results of this work show that glass with x = 0 has the highest shear, bulk and Young’s moduli which make it as suitable candidate for the manufacture of strong glass fibers in technological applications; but it should be mentioned that glass with x = 8 has higher handling temperature and super resistance against thermal attack.     

Calculation of the effect of pressurizing gases on the resonant modes of single-crystal parallelepiped

Resonant ultrasound spectroscopy provides for an experimental determination of the elastic moduli of a solid sample. The moduli are extracted by matching a theoretically computed resonant spectrum to the experimental vibrational spectrum. To determine the pressure dependence of the moduli, the vibrational spectrum can be taken with the sample in a pressurizing gas. Then the extraction of the intrinsic, pressure dependent moduli requires a theoretical treatment which permits removal of the perturbation of the spectrum due to the surface loading by the pressure and shear waves in the gas. In order to illustrate a treatment which accomplishes this removal, the theoretically computed frequency shifts and the quality factors are reported for two single-crystal parallelepiped pressurized by noble gases.     

Yield stresses and flow curves in metallic glass formers and granular systems

We discuss the concept of a glass transition line in the temperature-shear-stress plane in the context of recent simulation data for a metallic melt and dense-packed granular systems. Analyzing these data within a schematic model of the mode-coupling theory for dense glass formers under shear, values for the critical dynamic yield stress (the stress resulting in the limit of arbitrarily slow shear, at the glass transition) are estimated. We discuss two possible scenarios, that of a continuous rise in the dynamic yield stress at the transition, and that of a discontinuous transition, and discuss the data range that needs to be covered to decide between the two cases. A connection is made to the two commonly drawn versions of the jamming diagram, one convex and one concave regarding to the shape of the solid region.     

Low-frequency shear parameters of liquid viscoelastic materials

An experimental study of the shear parameters of viscoelastic liquids is carried out by the acoustic resonance method based on the changes in the natural frequency and Q factor of a piezoelectric quartz resonator. The liquid to be studied is placed between a stationary quartz strap and the piezoelectric quartz crystal vibrating at the resonance frequency. For a set of drilling muds, the values of the real and imaginary shear moduli are obtained at a frequency of 74 kHz. The measurements are performed with a liquid layer thickness much smaller than the shear wavelength. It is shown that the shear modulus decreases with increasing strain amplitude. A cluster model based on the Isakovich-Chaban nonlocal diffusion theory is proposed for explaining the low-frequency viscoelastic relaxation process.